WO2014007232A1 - Batterie secondaire à électrolyte non aqueux, module de batterie secondaire, et procédé d'utilisation de batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux, module de batterie secondaire, et procédé d'utilisation de batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2014007232A1
WO2014007232A1 PCT/JP2013/068099 JP2013068099W WO2014007232A1 WO 2014007232 A1 WO2014007232 A1 WO 2014007232A1 JP 2013068099 W JP2013068099 W JP 2013068099W WO 2014007232 A1 WO2014007232 A1 WO 2014007232A1
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negative electrode
secondary battery
electrolyte secondary
mpa
positive electrode
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PCT/JP2013/068099
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English (en)
Japanese (ja)
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充康 今▲崎▼
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株式会社カネカ
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Priority to JP2014523745A priority Critical patent/JP6136057B2/ja
Publication of WO2014007232A1 publication Critical patent/WO2014007232A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for using a nonaqueous electrolyte secondary battery, a secondary battery module, and a nonaqueous electrolyte secondary battery.
  • This application claims priority based on Japanese patent application: Japanese Patent Application No. 2012-150600.
  • Lithium ion storage batteries are currently widely used as power sources for mobile devices. Lithium ion storage batteries are expected to be used for large power supplies such as electric vehicles and power storage because of their higher energy density compared to existing nickel-cadmium storage batteries and nickel-hydrogen storage batteries. In particular, non-aqueous electrolyte secondary batteries using lithium titanate as a negative electrode active material are attracting attention because of their good cycle characteristics and high safety.
  • Patent Document 1 discloses a lithium battery that can be operated by applying a surface pressure to a positive electrode and a negative electrode in order to prevent brittle fracture of the battery material and a decrease in battery capacity associated with a charge / discharge cycle of the lithium battery. ing.
  • Patent Document 1 several lithium batteries focusing on pressure are disclosed (Patent Documents 2 to 4).
  • Non-aqueous electrolyte secondary batteries using lithium titanate as the negative electrode active material are attracting attention because of their good cycle characteristics and high safety (Patent Document 5).
  • JP 09-293499 A Japanese Patent Laid-Open No. 04-294071 Japanese Patent Laid-Open No. 01-035871 JP 2010-056070 A International Publication No. 2007/064043 Pamphlet
  • Titanium-based materials have almost no volume change due to charge / discharge, and brittle fracture of the material due to charge / discharge does not occur. However, there is no effect of improving the adhesion between the electrode / separator based on the volume change and the effect of stirring the electrolytic solution. For this reason, a battery using a titanium-based material for the negative electrode is disadvantageous in comparison with a battery using a conventional carbon-based negative electrode in terms of electric capacity and rate characteristics obtained during a steady cycle.
  • the present invention has been made in view of the above-described circumstances, and an object thereof is to provide a nonaqueous electrolyte secondary battery and a secondary battery module excellent in cycle characteristics and load characteristics. Another object of the present invention is to provide a method for using a non-aqueous electrolyte secondary battery that draws out excellent cycle characteristics and load characteristics.
  • the inventor applied a suitable pressure along the stacking direction of the power generating element including the positive electrode, the negative electrode, and the separator, It has been found that the characteristics and load characteristics are improved. Based on this finding, the present invention has been completed.
  • the non-aqueous electrolyte secondary battery of the present invention is a non-aqueous electrolyte secondary battery configured using a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte, and the operating potential of the negative electrode is based on a lithium standard (vs. Li + / Li) is 0.3 V or more and 2.5 V or less, and the negative electrode active material included in the negative electrode is a titanium-containing oxide, and a power generation element is configured including the positive electrode, the negative electrode, and a separator.
  • the positive electrode and the negative electrode may each have a thickness of 50 to 500 ⁇ m, and the pressure applied to the power generation element may be 0.5 MPa or more and 3.0 MPa or less.
  • the positive electrode and the negative electrode may each have a thickness of 500 to 5000 ⁇ m, and the pressure applied to the power generation element may be 0.005 MPa or more and 0.5 MPa or less.
  • the positive electrode and the negative electrode each have an area of 80 to 300 cm 2 .
  • the separator may be a nonwoven fabric.
  • the aperture ratio of the separator is preferably 50 to 95%.
  • the power generating element is formed by stacking a positive electrode, a separator, and a negative electrode, and pressure is applied in the stacking direction of the power generating element.
  • the power generation element may be covered with a laminate film.
  • the negative electrode active material may be titanium oxide, a material obtained by replacing a part of titanium with another element, and / or a lithium titanium composite oxide.
  • the non-aqueous electrolyte secondary battery of the present invention can be combined as necessary to form a secondary battery module.
  • the method of using the non-aqueous electrolyte secondary battery of the present invention is a method of using a non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte, and the operating potential of the negative electrode is based on lithium And 0.35 to 2.5 V, and the negative electrode active material contained in the negative electrode is a titanium-containing oxide. A pressure of 0.0 MPa or less is applied, and electric power generated from the power generation element is taken out.
  • the positive electrode and the negative electrode may each have a thickness of 50 to 500 ⁇ m, and the pressure applied to the power generation element may be 0.5 MPa or more and 3.0 MPa or less.
  • the positive electrode and the negative electrode may each have a thickness of 500 to 5000 ⁇ m, and the pressure applied to the power generation element may be 0.005 MPa or more and 0.5 MPa or less.
  • the liquid amount between the positive electrode and the negative electrode becomes uniform and uniform.
  • a nonaqueous electrolyte secondary battery that is pressurized and has excellent cycle characteristics can be realized. Further, since the distance between the electrodes is uniform and close, the load characteristics can be improved.
  • the negative electrode used in the nonaqueous electrolyte secondary battery of the present invention is composed of at least a negative electrode active material and a current collector.
  • the negative electrode may contain a conductive additive and a binder (binder) as necessary.
  • titanium oxide, lithium titanium oxide, or a part of titanium thereof operating at 0.3 V or more and 2.5 V or less on the basis of lithium (vs. Li + / Li) was replaced with another element. Things are used.
  • Li 4 Ti 5 O 12 , anatase TiO 2 , bronze TiO 2 (hereinafter referred to as TiO 2 (B)) and the like can be mentioned.
  • metals such as antimony, bismuth, tin, and indium that form an alloy with lithium at a potential of 0.3 V or more based on the lithium metal may be used. It is also possible to use a mixture of oxides having an insertion function at a potential of 0.3 V or more based on lithium metal, such as Nb 2 O 3 , WO 2 , and MoO 2 .
  • the binder may be mixed in the negative electrode.
  • the binder is not particularly limited.
  • at least one selected from the group consisting of polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), styrene-butadiene rubber, polyimide, acrylic, and derivatives thereof can be used. .
  • the binder is preferably dissolved or dispersed in a non-aqueous solvent or water from the viewpoint of ease of production of the negative electrode.
  • the non-aqueous solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, ethyl acetate, and tetrahydrofuran. You may add a dispersing agent and a thickener to these.
  • the amount of the binder contained in the negative electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the negative electrode active material. If it is the said range, the adhesiveness of a negative electrode active material and a conductive support material will be maintained, and adhesiveness with a collector can fully be acquired.
  • the conductive material may be contained in the negative electrode as necessary. Although it does not specifically limit as a conductive support material, A carbon material and / or a metal microparticle are preferable.
  • the carbon material include natural graphite, artificial graphite, vapor-grown carbon fiber, carbon nanotube, acetylene black, ketjen black, and furnace black.
  • the metal fine particles include copper, aluminum, nickel, and an alloy containing at least one of these. Further, the fine particles of inorganic material may be plated. These carbon materials and metal fine particles may be used alone or in combination of two or more.
  • the amount of the conductive additive contained in the negative electrode is preferably 0 to 30 parts by weight, more preferably 0 to 15 parts by weight with respect to 100 parts by weight of the negative electrode active material. If it is the said range, the electroconductivity of a negative electrode will be ensured favorable.
  • Examples of the current collector used in the negative electrode of the nonaqueous electrolyte secondary battery of the present invention include copper, aluminum, nickel, an alloy containing at least one of these, and a conductive polymer.
  • Examples of the shape include a foil shape, a mesh shape, a punching shape, an expanded shape, and a foam structure.
  • the porosity of the current collector is defined as “the sum of the inner volumes of the holes existing in the unit volume including the holes of the current collector”.
  • the mesh shape is a woven or unemployed cloth made of metal or conductive polymer fibers.
  • the thickness of the fiber is preferably 50 ⁇ m or more and 2000 ⁇ m or less. When the thickness is less than 50 ⁇ m, the strength of the current collector is weak. Therefore, when the active material mixture is supported on the current collector, the current collector tends to be easily broken. On the other hand, when a fiber thicker than 2000 ⁇ m is used, the opening becomes too large to obtain a preferable porosity, and it tends to be difficult to hold the active material mixture by the mesh.
  • the punching shape is a plate in which holes such as a circle, a rectangle, or a hexagon are formed, and a metal made of metal is punching metal. Since it is plate-shaped, it is defined by a void ratio in plan view, that is, “aperture ratio” (a ratio of the total area of holes per unit area of the plate in plan view).
  • the hole area ratio is determined by the ratio between the hole diameter and the bone (metal part), the hole shape, and the hole arrangement.
  • the shape of the hole is not particularly limited, but from the viewpoint of increasing the hole area ratio, a round hole staggered type (the staggered type has an opening angle of 60 °, for example) and a square hole parallel type are preferable.
  • “Expanded shape” refers to a staggered cut on a plate, which is stretched to form a mesh, and that made of metal is expanded metal.
  • the open area ratio is determined by the hole diameter and bone ratio, the hole shape, and the hole arrangement.
  • the foam structure has a three-dimensional network structure like a sponge, and the pores are continuous or dispersed. Its structure is determined by the number of pores per unit volume, the average pore size and the porosity. In the case of continuous holes, the shape and diameter of the holes are not particularly limited, but a structure having a high specific surface area is preferable.
  • the metal used in the current collector of the present invention is only required to be stable at the negative electrode operating voltage, preferably copper and its alloys when the operating potential is 0.7 V or less on the basis of lithium, and aluminum and its alloys when 0.7 V or more. Is preferred.
  • the negative electrode of the present invention is produced, for example, by supporting a negative electrode mixture comprising a negative electrode active material, a conductive additive, and a binder on a current collector.
  • a slurry is prepared with a negative electrode active material, a conductive additive, a binder, and a solvent. After the obtained slurry is filled and applied to the pores of the current collector and the outer surface thereof, the solvent is added.
  • the method of producing a negative electrode by removing is preferable.
  • the mixture of the negative electrode active material, the conductive additive and the binder may be supported on the current collector as it is without being dispersed in the solvent.
  • the method for preparing the slurry is not particularly limited, but since the negative electrode active material, the conductive additive, the binder, and the solvent can be mixed uniformly, a ball mill, a planetary mixer, a jet mill, a thin film swirl mixer, and a stirring and mixing granulator are provided. It is preferable to use it.
  • the method for kneading the slurry is not particularly limited, but the slurry may be prepared by mixing the negative electrode active material, the conductive additive, and the binder and then adding the solvent, or the negative electrode active material, the conductive additive, the binder, and the solvent may be combined together. You may mix and produce.
  • the solid content concentration of the slurry is preferably 30 wt% or more and 90 wt% or less. If it is less than 30 wt%, the viscosity of the slurry tends to be too low, whereas if it is higher than 90 wt%, the viscosity of the slurry tends to be too high, and it may be difficult to form an electrode described later.
  • the solvent used for the slurry is preferably a non-aqueous solvent or water.
  • the non-aqueous solvent is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, methyl ethyl ketone, methyl acetate, ethyl acetate, and tetrahydrofuran.
  • NMP N-methyl-2-pyrrolidone
  • dimethylformamide dimethylacetamide
  • methyl ethyl ketone methyl acetate
  • ethyl acetate etrahydrofuran.
  • the method for supporting the negative electrode mixture on the current collector is not particularly limited, but for example, a method of removing the solvent after applying the slurry with a doctor blade, die coater, comma coater, etc., or a method of removing the solvent after adhering to the current collector by spraying.
  • a method of removing, a method of removing the solvent after impregnating the current collector in the slurry, and a method of removing the solvent after preparing a sheet with only the negative electrode mixture and attaching the sheet to the current collector are preferred.
  • the method for removing the solvent is preferable because it is easy to dry using an oven or a vacuum oven. Examples of the atmosphere include room temperature or high temperature air, an inert gas, and a vacuum state.
  • the negative electrode may be formed before or after forming the positive electrode described later.
  • the negative electrode active material, conductive additive and binder When the negative electrode active material, conductive additive and binder are not dispersed in the solvent, the negative electrode active material, conductive additive and binder can be mixed uniformly, so use a ball mill, planetary mixer, jet mill, or thin-film swirl mixer. After preparing the mixture, it is preferable to carry the mixture on the current collector.
  • a method of supporting the mixture on the current collector is not particularly limited, but a method of pressing the mixture after filling the current collector is preferable. When pressing, it may be heated. Moreover, you may compress a negative electrode using a roll press machine etc. after negative electrode preparation. The electrode may be compressed before or after the positive electrode described later is formed.
  • the positive electrode used in the nonaqueous electrolyte secondary battery of the present invention is composed of at least a positive electrode mixture and a current collector.
  • a positive electrode mixture contains a positive electrode active material and a binder at least, and a conductive support material as needed.
  • the positive electrode active material is not particularly limited, but is at least one selected from the group consisting of composite oxides, composite nitrides, composite fluorides, composite sulfides, composite selenides and the like containing alkali metals and / or alkaline earth metals. Seeds can be used. In particular, since the cycle stability is excellent, it is preferable to include a lithium manganese compound.
  • the lithium manganese compound for example, Li 2 MnO 3, Li a M b Mn 1-b N c O 4 (0 ⁇ a ⁇ 2,0 ⁇ b ⁇ 0.5,1 ⁇ c ⁇ 2, M 2 to Li 1+ , at least one selected from the group consisting of elements belonging to Group 13 and belonging to the third and fourth periods, N being at least one selected from the group consisting of elements belonging to Groups 14 to 16 and belonging to the third period) x M y Mn 2-xy O 4 (0 ⁇ x ⁇ 0.34,0 ⁇ y ⁇ 0.6, at least 1 M is selected from the group consisting of elements belonging to a and the third to fourth period 2-13 group A lithium manganese compound represented by Species).
  • M is at least one selected from elements belonging to the groups 2 to 13 and belonging to the 3rd to 4th periods, but Al, Mg, Zn, Ni, Co, Fe and Cr are preferred, Al, Mg, Zn, Ni and Cr are more preferred, and Al, Mg, Zn and Ni are even more preferred.
  • N is preferably Si, P, or S because the effect of improving the stability is large.
  • the positive electrode active material layer may contain a binder. What was illustrated by the binder used for the negative electrode mixture mentioned above is applicable similarly.
  • the binder is preferably dissolved or dispersed in a non-aqueous solvent or water from the viewpoint of easy production of the positive electrode.
  • a non-aqueous solvent those exemplified above for the non-aqueous solvent can be similarly applied. You may add a dispersing agent and a thickener to these.
  • the positive electrode may contain a conductive additive as necessary. Although it does not specifically limit as a conductive support material, A carbon material or a metal microparticle is preferable. Examples of the carbon material include the same type as the carbon material that can be contained in the negative electrode. Examples of the metal fine particles include aluminum and aluminum alloys. Further, the fine particles of inorganic material may be plated. These carbon materials and metal fine particles may be used alone or in combination of two or more.
  • the amount of the conductive additive contained in the positive electrode is preferably 1 part by weight or more and 30 parts by weight or less, more preferably 1 part by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the positive electrode active material. If it is this range, the electroconductivity of a positive electrode will be ensured favorable. Moreover, adhesiveness with a binder is maintained and sufficient adhesiveness with a collector can be obtained. On the other hand, when a larger amount of conductive aid than 30 parts by weight is used, the volume occupied by the conductive aid increases and the energy density tends to decrease.
  • the positive electrode is produced by, for example, supporting a positive electrode active material, a conductive additive, and a positive electrode active material layer of a binder on a current collector. From the ease of the production method, the positive electrode active material, the conductive additive, the binder, A slurry is prepared with a solvent, and after filling and applying the obtained slurry to the pores and the outer surface of the current collector, a positive electrode is prepared by removing the solvent, or a sheet is prepared only with the positive electrode mixture. A method of removing the solvent after pasting to the current collector is preferable. Alternatively, the mixture of the positive electrode active material, the conductive additive and the binder may be supported on the current collector as it is without being dispersed in the solvent.
  • the method for preparing the slurry, the solid content concentration of the slurry, the solvent used for the slurry, the method for supporting the active material layer on the current collector, and the compression of the electrode can be similarly applied to the preparation of the positive electrode. .
  • Capacity ratio and area ratio of negative electrode to positive electrode, thickness> The ratio of the electric capacity of the positive electrode and the electric capacity of the negative electrode in the nonaqueous electrolyte secondary battery of the present invention preferably satisfies the following formula (1).
  • A shows the electrical capacity per 1 cm ⁇ 2 > of positive electrodes
  • B shows the electrical capacity per 1 cm ⁇ 2 > of negative electrodes.
  • the potential of the negative electrode may become the deposition potential of alkali metal and / or alkaline earth metal during overcharge, while B / A is greater than 1.3. Side reactions may occur because there are many negative electrode active materials not involved in the battery reaction.
  • the area of the positive electrode and the negative electrode in the nonaqueous electrolyte secondary battery of the present invention is preferably 80 cm 2 or more and 300 cm 2 or less. When it is smaller than 80 cm 2, the productivity of the electrode and the battery is lowered, and when it is 300 cm 2 or more, it tends to be difficult to press uniformly.
  • the area ratio between the positive electrode and the negative electrode in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, but preferably satisfies the following formula (2).
  • the area ratio between the separator and the negative electrode used in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, but preferably satisfies the following formula (3).
  • the thickness of the positive electrode and the negative electrode in the nonaqueous electrolyte secondary battery of the present invention is preferably 50 ⁇ m or more and 5 mm or less.
  • An electrode of 50 ⁇ m or less is difficult to manufacture, and an electrode of 5 mm or more has a tendency that the designed capacity cannot be developed because lithium ions diffuse slowly.
  • An electrode is manufactured by a filling method.
  • separator used in the non-aqueous electrolyte secondary battery of the present invention include porous materials and nonwoven fabrics, but the nonwoven fabric is capable of adjusting lithium ion mobility by adjusting the porosity and productivity and cost. Is preferred.
  • the porosity of the separator is preferably 50% or more and 95% or less. When the open area ratio is less than 50%, the gap between the electrodes becomes small at the time of pressurization and the liquid retaining property is lowered, so that the cycle property is lowered. On the other hand, when it is 95% or more, the hole tends to be too large to cause an internal short circuit.
  • the material of the nonwoven fabric separator is preferably one that does not dissolve in the organic solvent constituting the electrolytic solution.
  • a polyolefin polymer such as polyethylene or polypropylene
  • a polyester polymer such as polyethylene terephthalate
  • cellulose such as polyethylene terephthalate
  • polyvinyl alcohol such as polyvinyl alcohol
  • inorganic materials such as glass.
  • the thickness of the separator is preferably 1 to 500 ⁇ m. If it is less than 1 ⁇ m, it tends to break due to insufficient mechanical strength of the separator and cause an internal short circuit. On the other hand, when it is thicker than 500 ⁇ m, the load characteristics of the battery tend to be reduced due to the increase in the internal resistance of the battery and the distance between the positive and negative electrodes. A more preferred thickness is 10 to 50 ⁇ m.
  • Non-aqueous electrolyte used in the non-aqueous electrolyte secondary battery of the present invention is not particularly limited, but a polymer is impregnated with an electrolytic solution in which a solute is dissolved in a non-aqueous solvent, or an electrolytic solution in which a solute is dissolved in a non-aqueous solvent.
  • a gel electrolyte or the like can be used.
  • the non-aqueous solvent preferably contains a cyclic aprotic solvent and / or a chain aprotic solvent.
  • a cyclic aprotic solvent include cyclic carbonates, cyclic esters, cyclic sulfones and cyclic ethers.
  • chain aprotic solvent include chain carbonates, chain carboxylic acid esters and chain ethers.
  • a solvent generally used as a solvent for nonaqueous electrolytes such as acetonitrile may be used.
  • dimethyl carbonate, methyl ethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethylene carbonate, fluoroethylene carbonate, propylene carbonate, butylene carbonate, tetrahydrofuran, ⁇ -butyrolactone, 1,2-dimethoxyethane, Sulfolane, dioxolane, methyl propionate and the like can be used.
  • These solvents may be used alone or as a mixture of two or more. However, in view of the ease of dissolving the solute described below and the high conductivity of lithium ions, a mixture of two or more of these solvents. Is preferably used.
  • a gel electrolyte in which an electrolyte is impregnated in a polymer can also be used.
  • the solute is not particularly limited.
  • lithium salts such as LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiCF 3 SO 3 , LiBOB (Lithium Bis (Oxalato) Borate), LiN (SO 2 CF 3 ) 2
  • Sodium salts such as NaClO 4 , NaBF 4 , NaPF 6
  • magnesium salts such as Mg (ClO 4 ) 2 , Mg [AlCl 2 (C 4 H 9 ) (C 2 H 5 )] 2 , C 6 H 5 MgCl are solvents. It is preferable because it is easy to dissolve in.
  • the concentration of the solute contained in the electrolytic solution is preferably 0.5 mol / L or more and 2.0 mol / L or less. If it is less than 0.5 mol / L, the desired ionic conductivity may not be exhibited. On the other hand, if it is higher than 2.0 mol / L, the solute may not be dissolved any more, and the viscosity increases and the load characteristic decreases. To do.
  • the non-aqueous electrolyte may contain a trace amount of additives such as a flame retardant and a stabilizer.
  • Non-aqueous electrolyte secondary battery The positive electrode and the negative electrode of the non-aqueous electrolyte secondary battery of the present invention may be in the form in which the same electrode is formed on both sides of the current collector. Alternatively, it may be a bipolar electrode.
  • a conductive material and / or an insulating material is disposed between the positive electrode and the negative electrode in order to prevent a liquid junction between the positive electrode and the negative electrode through the current collector.
  • a separator is disposed between the positive electrode side and the negative electrode side of the adjacent bipolar electrode, and the positive electrode and An insulating material is disposed around the negative electrode.
  • the nonaqueous electrolyte secondary battery of the present invention is a laminate in which separators are disposed between the positive electrode side and the negative electrode side.
  • the positive electrode, the negative electrode, and the separator are impregnated with a nonaqueous electrolyte that is responsible for ionic conduction.
  • the electrolyte may be impregnated in the positive electrode and the negative electrode, or may be in a state only between the positive electrode and the negative electrode. If the positive electrode and the negative electrode are not in direct contact with the gel electrolyte, it is not always necessary to use a separator.
  • the amount of the nonaqueous electrolyte used in the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, but is preferably 0.1 mL or more per 1 Ah of battery capacity. If it is less than 0.1 mL, the conduction of lithium ions accompanying the electrode reaction may not catch up, and the desired battery performance may not be exhibited.
  • the nonaqueous electrolyte may be included in the positive electrode, the negative electrode, and the separator in advance, or may be added after laminating a separator disposed between the positive electrode side and the negative electrode side.
  • a gel-like non-aqueous electrolyte it may be gelled after impregnation with a monomer, or may be placed between the positive electrode and the negative electrode after gelling in advance.
  • the laminate is packaged with a laminate film.
  • the exterior may be provided with a mechanism for releasing the generated gas or the like. Further, a mechanism for injecting an additive for recovering the function of the deteriorated nonaqueous electrolyte secondary battery from the outside of the battery may be provided.
  • the number of stacked layers can be stacked until a desired battery capacity is exhibited. According to the present invention, when stacking, pressure is applied in the stacking direction of the power generating elements.
  • the pressurizing method is not limited as long as the electrode surface is uniformly pressed.
  • the pressurization method includes an internal pressurization in which a pressurizing member is disposed inside the cell and pressurizes, and an external pressurization that pressurizes through the exterior of the cell.
  • a metal plate or a resin plate is installed on the electrode surface, and an elastic member such as a rubber or a spring is disposed inside the cell, so that uniform pressurization can be performed.
  • the spring include a coil spring, a disc spring, and a leaf spring.
  • a tension spring may be used as means for pulling both ends of the laminate.
  • the exterior may be formed of a member such as metal, resin, or rubber that is elastically deformed, and pressure may be applied to the cell using the elasticity of the exterior itself.
  • an elastic member such as a spring or rubber may be disposed outside the exterior so that pressure is applied from the outside of the exterior.
  • the appropriate range of pressure applied to the electrode is 0.005 MPa to 3.0 MPa.
  • a pressure range of 0.5 MPa to 3 MPa is preferable, and when the electrode thickness is 500 ⁇ m or more and 5 mm or less, a pressure range of 0.005 MPa to 0.5 MPa is preferable.
  • the appropriate applied pressure is smaller as the electrode thickness is larger is that for batteries of the same capacity, the thicker the electrode, the smaller the number of electrodes and the less free space between the electrodes and the separator. It can be considered that has decreased.
  • the performance is deteriorated. This is probably because the distance between the electrodes increases due to the low pressure and the ion distribution becomes non-uniform so that side reactions occur and the capacity retention rate decreases. Further, the performance deteriorates when the pressure is larger than the pressure range. This can be considered that the amount of electrolyte solution between the electrodes decreases due to excessive pressurization and the capacity retention rate decreases.
  • the non-aqueous electrolyte secondary battery of the present invention can be a secondary battery module by connecting a plurality of non-aqueous electrolyte secondary batteries.
  • the secondary battery module can be produced by appropriately connecting nonaqueous electrolyte secondary batteries in series and in parallel according to the desired size, capacity, and voltage.
  • the individual battery cells may be pressurized or the battery group made into the secondary battery module may be collectively pressurized.
  • a control circuit is attached to the secondary battery module in order to check the state of charge of each battery and improve safety.
  • titanium dioxide and lithium hydroxide are mixed so that the molar ratio of titanium and lithium is 5: 4, and then this mixture is heated at 800 ° C. for 12 hours in a nitrogen atmosphere to obtain a negative electrode active material. Produced.
  • the electrode production method was changed as follows.
  • Cathode active material Li 1.1 Al 0.1 Mn 1.8 O 4 is published in the literature "Lithium Aluminum Manganese Oxide Having Spinel-Framework Structure for Long-Life Lithium-Ion Batteries” Electrochemical and Solid-State Letters Volume 9, Issue 12, Pages A557 (2006) Prepared by the method described.
  • an aqueous dispersion of manganese dioxide, lithium carbonate, aluminum hydroxide, and boric acid was prepared, and a mixed powder was prepared by a spray drying method.
  • the amounts of manganese dioxide, lithium carbonate and aluminum hydroxide were adjusted so that the molar ratio of lithium, aluminum and manganese was 1.1: 0.1: 1.8.
  • the mixed powder was heated at 900 ° C. for 12 hours in an air atmosphere, and then again heated at 650 ° C. for 24 hours. Finally, the powder was washed with water at 95 ° C. and dried to prepare a positive electrode active material.
  • this positive electrode active material 100 parts by weight of this positive electrode active material, 3.2 parts by weight of a conductive additive (acetylene black), and solid content of PVdF binder (KF7305, manufactured by Kureha Chemical Co., Ltd.) (solid content concentration 5 wt%, NMP solution) In terms of 3.2 parts by weight.
  • a conductive additive acetylene black
  • solid content of PVdF binder KF7305, manufactured by Kureha Chemical Co., Ltd.
  • solid content concentration 5 wt%, NMP solution solid content concentration 5 wt%, NMP solution
  • the electrode preparation method was changed as follows.
  • the produced negative electrode and positive electrode were each punched into 16 mm ⁇ and used as working electrodes.
  • Alkali metal or alkaline earth metal was punched out to 16 mm ⁇ and used as a counter electrode.
  • a working electrode / separator manufactured by Polypore Co., Ltd.
  • a half cell was prepared by adding 0.2 mL of 1 mol / L of an alkali metal salt or alkaline earth metal salt dissolved in a / 70 vol% non-aqueous solvent. The half-cell was allowed to stand at 25 ° C.
  • the capacity per 1 g of the positive electrode active material was 100 mAh
  • the capacity per 1 g of the negative electrode active material was 165 mAh.
  • a similar experiment was conducted with a current value of 1/8 C (referring to a current value of 1/8 when the current value at which charging or discharging is completed in 1 hour is 1 C). It was possible to obtain an equivalent capacity.
  • FIG. 1 shows a cross-sectional view of the produced nonaqueous electrolyte secondary battery.
  • a positive electrode (shown by 11) and a negative electrode (shown by 13) prepared according to the above procedure (1) were prepared and laminated in the order of positive electrode 11 / separator 12 / negative electrode 13.
  • the separator 12 two cellulose non-woven fabrics (opening ratio: 50%, thickness: 25 ⁇ m) were used in an overlapping manner.
  • the size of the positive electrode 11 was 10.0 cm ⁇ 10.0 cm and the thickness was 150 ⁇ m
  • the size of the negative electrode 13 was 10.5 cm ⁇ 10.5 cm
  • the thickness was 110 ⁇ m
  • the size of the separator 12 was 11.0 cm ⁇ 11.0 cm.
  • aluminum tabs serving as lead electrodes 15 and 16 were vibration welded to the positive electrode 11 and the negative electrode 12, and then placed in a bag-like aluminum laminate sheet 17.
  • a nonaqueous electrolyte secondary battery was produced by heat sealing together.
  • a pressure sensitive paper 23 pressure measurement film “Prescale” manufactured by Fuji Film Co., Ltd .; for low pressure, for ultra-low pressure, for ultra-low pressure
  • the laminate 21 , 22 were tightened with bolts to pressurize from the stacking direction (vertical direction in the case of FIG. 1). Based on the result of measuring the pressure P with the pressure sensitive paper 23, the measurement conditions were set.
  • Capacity maintenance rate (discharge capacity at 300 cycles / discharge capacity at one cycle) ⁇ 100 Table 1 shows the relationship between the measured capacity retention rate and pressure.
  • the capacity maintenance rate of each battery reaches 90%.
  • the average value of the capacity retention rate of the five batteries at 0.5 MPa or more and 3 MPa or less is 92.9, and the deviation from the average value of the capacity maintenance rate of each battery is within ⁇ 2%, so that the stable capacity maintenance is maintained. Showed the rate.
  • Table 2 shows the rate characteristic measurement results at each pressure.
  • the rate characteristics were evaluated as a ratio to the discharge capacity at 0.2C.
  • the characteristics are lower than 0.5 MPa at each rate. This is considered to be caused by a long distance between the electrodes.
  • the rate characteristic at 4 MPa is not significantly reduced as compared with the rate characteristic at 3 MPa.
  • the layers were laminated in the order of positive electrode / separator / negative electrode.
  • As the separator two cellulose non-woven fabrics (opening ratio: 50%, thickness: 25 ⁇ m) were used.
  • the size of the positive electrode was 10.0 cm ⁇ 10.0 cm
  • the thickness was 1400 ⁇ m
  • the size of the negative electrode was 10.5 cm ⁇ 10.5 cm
  • the thickness was 1200 ⁇ m
  • the size of the separator was 11.0 cm ⁇ 11.0 cm.
  • an aluminum tab serving as a lead electrode was vibration welded to the positive electrode and the negative electrode, and then placed in a bag-shaped aluminum laminate film.
  • the outlet of the bag was heat sealed together with the extraction electrode.
  • Capacity maintenance rate (discharge capacity at 50 cycles / discharge capacity at one cycle) ⁇ 100
  • Table 3 shows the relationship between the measured capacity retention rate and pressure.
  • Table 4 shows the rate characteristic measurement results at each pressure.
  • the rate characteristics were evaluated as a ratio to the discharge capacity at 1 / 8C.
  • the characteristics are lower than 0.005 MPa at each rate. This is considered to be caused by a long distance between the electrodes.
  • the rate characteristic at 1 MPa is slightly lower than the rate characteristic at 0.5 MPa. This is considered that the electrolyte solution between electrodes is pushed out and it is in the condition near liquid drainage.
  • the present invention is not limited to the above-described embodiments.
  • the present invention is also applied to a non-aqueous electrolyte secondary battery as a finished product manufactured by introducing a device or a machine that applies pressure in the battery.
  • Other modifications may be made as appropriate without departing from the essence of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Battery Mounting, Suspending (AREA)

Abstract

L'invention concerne une batterie secondaire à électrolyte non aqueux qui comprend un élément de génération d'énergie électrique qui est constitué d'une électrode positive (11), d'une électrode négative (13) et d'un séparateur (12), le potentiel de fonctionnement de l'électrode négative (13) étant de 0,3 V à 2,5 V (inclus) sur la base du lithium. Cette batterie secondaire à électrolyte non aqueux utilise un oxyde contenant du titane, et une pression de 0,5 MPa à 3 MPa (inclus) est appliquée à l'élément de génération d'énergie électrique dans la direction de stratification de celui-ci. Cette batterie secondaire à électrolyte non aqueux possède des caractéristiques de cycle améliorées et des caractéristiques de débit améliorées.
PCT/JP2013/068099 2012-07-04 2013-07-02 Batterie secondaire à électrolyte non aqueux, module de batterie secondaire, et procédé d'utilisation de batterie secondaire à électrolyte non aqueux WO2014007232A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018131094A1 (fr) * 2017-01-11 2018-07-19 エス・イー・アイ株式会社 Dispositif électrochimique
JP2019160512A (ja) * 2018-03-12 2019-09-19 三洋化成工業株式会社 リチウムイオン電池の製造方法
WO2020004343A1 (fr) * 2018-06-26 2020-01-02 日立化成株式会社 Batterie secondaire et procédé de fabrication associé

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7391799B2 (ja) * 2020-08-27 2023-12-05 株式会社東芝 二次電池、電池パック、車両及び定置用電源

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JPS6435871A (en) * 1987-07-31 1989-02-06 Nippon Telegraph & Telephone Lithium secondary cell
JPH04294071A (ja) * 1991-03-22 1992-10-19 Yuasa Corp リチウム電池
JP2001143702A (ja) * 1999-11-10 2001-05-25 Sumitomo Electric Ind Ltd 非水二次電池
JP2002289189A (ja) * 2001-03-23 2002-10-04 Hitachi Maxell Ltd 非水電池
JP2008021556A (ja) * 2006-07-13 2008-01-31 Sharp Corp リチウム二次電池及びその製造方法
JP2010056070A (ja) * 2008-07-30 2010-03-11 Idemitsu Kosan Co Ltd 全固体二次電池及びそれを備えてなる装置
JP2012256584A (ja) * 2011-02-18 2012-12-27 Sumitomo Electric Ind Ltd 電気化学素子

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6435871A (en) * 1987-07-31 1989-02-06 Nippon Telegraph & Telephone Lithium secondary cell
JPH04294071A (ja) * 1991-03-22 1992-10-19 Yuasa Corp リチウム電池
JP2001143702A (ja) * 1999-11-10 2001-05-25 Sumitomo Electric Ind Ltd 非水二次電池
JP2002289189A (ja) * 2001-03-23 2002-10-04 Hitachi Maxell Ltd 非水電池
JP2008021556A (ja) * 2006-07-13 2008-01-31 Sharp Corp リチウム二次電池及びその製造方法
JP2010056070A (ja) * 2008-07-30 2010-03-11 Idemitsu Kosan Co Ltd 全固体二次電池及びそれを備えてなる装置
JP2012256584A (ja) * 2011-02-18 2012-12-27 Sumitomo Electric Ind Ltd 電気化学素子

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018131094A1 (fr) * 2017-01-11 2018-07-19 エス・イー・アイ株式会社 Dispositif électrochimique
JP2019160512A (ja) * 2018-03-12 2019-09-19 三洋化成工業株式会社 リチウムイオン電池の製造方法
JP7034777B2 (ja) 2018-03-12 2022-03-14 三洋化成工業株式会社 リチウムイオン電池の製造方法
WO2020004343A1 (fr) * 2018-06-26 2020-01-02 日立化成株式会社 Batterie secondaire et procédé de fabrication associé
JPWO2020004343A1 (ja) * 2018-06-26 2021-07-15 昭和電工マテリアルズ株式会社 二次電池及びその製造方法

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